Charge transfer effects on Fe 2p X-ray photoemission of RbMn[Fe(CN) 6], K3Fe(CN)6, and K4Fe(CN)6

Yusuke Nanba, Kozo Okada

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

In the studies on the valence transition in RbMn[Fe(CN)6], the Fe valence was determined by observing the binding energy of the primary Fe 2p photoemission line, while the detailed analysis of the whole Fe 2p X-ray photoemission spectrum (XPS) has not so far been performed both experimentally and theoretically. In the present study, the Fe 2p XPS is calculated for [Fe(CN)6]3- and [Fe(CN)6]4- cluster models by a configuration-interaction full-multiplet theory. The result shows that the line shape of the Fe 2p XPS is affected by ligand-to-metal charge transfer (LMCT) and intraatomic multiplet coupling. It is in clear contrast to the Fe 2p X-ray photoabsorption spectrum (XAS), where metal-toligand charge transfer (MLCT) plays an important role. It is clearly shown that the difference in the ground-state wavefunction between the [Fe(CN)6]3- and [Fe(CN)6]4- clusters is reflected in the CT satellite structures and the multiplet structures in the Fe 2p XPS. From the analysis of the observed Fe 2p XPS, together with the analysis of the Fe 2p XAS, we conclude that the Fe 3d energy level relative to the C 2p energy level in RbMn[Fe(CN)6] is considerably larger than that in K 3Fe(CN)6.

Original languageEnglish
Article number074710
JournalJournal of the Physical Society of Japan
Volume80
Issue number7
DOIs
Publication statusPublished - Jul 2011

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photoelectric emission
charge transfer
x rays
fine structure
photoabsorption
energy levels
valence
metals
configuration interaction
line shape
binding energy
ligands
ground state

Keywords

  • 2p spin-orbit splitting
  • Fe 2p X-ray photoemission
  • K Fe(CN)
  • KFe(CN)
  • LMCT
  • MLCT
  • RbMn[Fe(CN)]
  • T2g orbital

ASJC Scopus subject areas

  • Physics and Astronomy(all)

Cite this

Charge transfer effects on Fe 2p X-ray photoemission of RbMn[Fe(CN) 6], K3Fe(CN)6, and K4Fe(CN)6. / Nanba, Yusuke; Okada, Kozo.

In: Journal of the Physical Society of Japan, Vol. 80, No. 7, 074710, 07.2011.

Research output: Contribution to journalArticle

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abstract = "In the studies on the valence transition in RbMn[Fe(CN)6], the Fe valence was determined by observing the binding energy of the primary Fe 2p photoemission line, while the detailed analysis of the whole Fe 2p X-ray photoemission spectrum (XPS) has not so far been performed both experimentally and theoretically. In the present study, the Fe 2p XPS is calculated for [Fe(CN)6]3- and [Fe(CN)6]4- cluster models by a configuration-interaction full-multiplet theory. The result shows that the line shape of the Fe 2p XPS is affected by ligand-to-metal charge transfer (LMCT) and intraatomic multiplet coupling. It is in clear contrast to the Fe 2p X-ray photoabsorption spectrum (XAS), where metal-toligand charge transfer (MLCT) plays an important role. It is clearly shown that the difference in the ground-state wavefunction between the [Fe(CN)6]3- and [Fe(CN)6]4- clusters is reflected in the CT satellite structures and the multiplet structures in the Fe 2p XPS. From the analysis of the observed Fe 2p XPS, together with the analysis of the Fe 2p XAS, we conclude that the Fe 3d energy level relative to the C 2p energy level in RbMn[Fe(CN)6] is considerably larger than that in K 3Fe(CN)6.",
keywords = "2p spin-orbit splitting, Fe 2p X-ray photoemission, K Fe(CN), KFe(CN), LMCT, MLCT, RbMn[Fe(CN)], T2g orbital",
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AB - In the studies on the valence transition in RbMn[Fe(CN)6], the Fe valence was determined by observing the binding energy of the primary Fe 2p photoemission line, while the detailed analysis of the whole Fe 2p X-ray photoemission spectrum (XPS) has not so far been performed both experimentally and theoretically. In the present study, the Fe 2p XPS is calculated for [Fe(CN)6]3- and [Fe(CN)6]4- cluster models by a configuration-interaction full-multiplet theory. The result shows that the line shape of the Fe 2p XPS is affected by ligand-to-metal charge transfer (LMCT) and intraatomic multiplet coupling. It is in clear contrast to the Fe 2p X-ray photoabsorption spectrum (XAS), where metal-toligand charge transfer (MLCT) plays an important role. It is clearly shown that the difference in the ground-state wavefunction between the [Fe(CN)6]3- and [Fe(CN)6]4- clusters is reflected in the CT satellite structures and the multiplet structures in the Fe 2p XPS. From the analysis of the observed Fe 2p XPS, together with the analysis of the Fe 2p XAS, we conclude that the Fe 3d energy level relative to the C 2p energy level in RbMn[Fe(CN)6] is considerably larger than that in K 3Fe(CN)6.

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